CN107774315B - Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation - Google Patents
Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation Download PDFInfo
- Publication number
- CN107774315B CN107774315B CN201610750944.XA CN201610750944A CN107774315B CN 107774315 B CN107774315 B CN 107774315B CN 201610750944 A CN201610750944 A CN 201610750944A CN 107774315 B CN107774315 B CN 107774315B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- salt
- reaction
- bromine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 17
- 239000007791 liquid phase Substances 0.000 title claims abstract description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 42
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- -1 lanthanide salt Chemical class 0.000 claims abstract description 11
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 62
- 239000007789 gas Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- OZTBHAGJSKTDGM-UHFFFAOYSA-N 9,10-dioxoanthracene-1,5-disulfonic acid Chemical compound O=C1C=2C(S(=O)(=O)O)=CC=CC=2C(=O)C2=C1C=CC=C2S(O)(=O)=O OZTBHAGJSKTDGM-UHFFFAOYSA-N 0.000 claims description 11
- OKONMFPEKSWGEU-UHFFFAOYSA-N 9,10-dioxoanthracene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 OKONMFPEKSWGEU-UHFFFAOYSA-N 0.000 claims description 11
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011572 manganese Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001503 inorganic bromide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 150000002603 lanthanum Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- DNDPPWHDBXKSGJ-UHFFFAOYSA-N 1,1,1,2-tetrabromopropane Chemical compound CC(Br)C(Br)(Br)Br DNDPPWHDBXKSGJ-UHFFFAOYSA-N 0.000 claims description 2
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 85
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 80
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 80
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 78
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 34
- 239000007787 solid Substances 0.000 description 34
- 238000003756 stirring Methods 0.000 description 34
- 238000004458 analytical method Methods 0.000 description 32
- 239000000463 material Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical compound BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 18
- 239000005711 Benzoic acid Substances 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 235000010233 benzoic acid Nutrition 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- 239000012535 impurity Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 18
- NJESAXZANHETJV-UHFFFAOYSA-N 4-methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 17
- 238000001816 cooling Methods 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 238000007789 sealing Methods 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JXKZURFTWZXOOD-UHFFFAOYSA-N 1,1,2,2-tetrabromopropane Chemical compound CC(Br)(Br)C(Br)Br JXKZURFTWZXOOD-UHFFFAOYSA-N 0.000 description 1
- MVIAXEGUXPAUPQ-UHFFFAOYSA-N 2,2,3,3-tetrabromobutane Chemical compound CC(Br)(Br)C(C)(Br)Br MVIAXEGUXPAUPQ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical group [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing aromatic polycarboxylic acid by liquid-phase oxidation, which mainly solves the problem that the bromine dosage in the catalyst is too high when the aromatic polycarboxylic acid is prepared by liquid-phase oxidation of polyalkyl substituted aromatic hydrocarbon in the prior art. The catalyst for preparing the aromatic polycarboxylic acid by liquid-phase oxidation comprises Co salt, Mn salt, lanthanide salt and a bromine-containing compound, wherein the Co salt, Mn salt, lanthanide salt and Br are 500 (200-300) (20-110) (1000-2000) by weight, so that the technical problem is better solved, and the catalyst can be used for preparing the aromatic polycarboxylic acid by liquid-phase oxidation of polyalkyl substituted aromatic hydrocarbon.
Description
Technical Field
The invention relates to a catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation.
Background
Purified terephthalic acid, commonly known as PTA, is a basic raw material for synthesizing polyethylene terephthalate (PET), and the demand thereof is continuously increasing, and it is expected that the global demand for PTA will reach 5000 ten thousand tons in 2015. At present, the PTA production technology is mainly a two-step process of p-xylene (PX) oxidation and hydrofining developed by Amoco-MC company, wherein a Co-Mn-Br catalyst system is adopted in the oxidation step, and acetic acid is used as a solvent; hydrogenation is mainly carried out by adding p-aldehyde benzoic acid (4-CBA) into p-methyl benzoic acid (p-TA), centrifuging and washing with water to remove.
In the development process of the PTA production process, four main patent technologies of Amoco, Mitsui, ICI and Eastman are formed. The four technologies have the common point that the four technologies all adopt an Amoco-MC liquid phase catalytic oxidation method, the catalyst is a cobalt-manganese-bromine system, the solvent is acetic acid, and the difference is that the oxidation reaction temperature of various technologies is different (from 160 ℃ to 225 ℃), and the corresponding process conditions, the reactor forms and the process design are also different. ICI and Amoco reaction temperature is highest, the three-well-Amoco temperature is intermediate, and Eastman is lowest, which are respectively called high temperature oxidation, medium temperature oxidation and low temperature oxidation process.
No matter which process is adopted, bromine is needed as a cocatalyst, the bromine has strong corrosivity, and particularly under the high-temperature condition, so all reactors adopt expensive titanium materials; at the same time, too much bromine causes side reactions to occur, resulting in loss of solvent and raw materials. Many scholars both at home and abroad are studying to reduce the bromine content or completely replace bromine. U.S. Pat. No. 4,7985875 (Process for preparing aromatic polycarboxylic acid by liquid alkylation) describes a Process in which a bromine-containing ionic liquid is used as a promoter to achieve the same effect as a conventional catalyst, but this does not substantially reduce the bromine content. U.S. Pat. No. 6,790 (Method to produced aromatic dicarboxylic acids using cobalt and zirconium catalysts) uses cobalt and cerium as catalysts in a molar ratio of 7:1 without the use of a bromine source, with a terephthalic acid yield of greater than 95%; however, the catalyst is used in an amount of more than 5 wt%.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of high bromine content in the catalyst in the prior art, and provides a catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation of polyalkyl-substituted aromatic hydrocarbon, which has the characteristics of low bromine consumption, high yield of target products and low impurity content.
The second technical problem to be solved by the present invention is a method for preparing aromatic polycarboxylic acid by liquid phase oxidation using the catalyst described in the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for preparing the aromatic polycarboxylic acid by liquid-phase oxidation comprises Co salt, Mn salt, lanthanide salt and a bromine-containing compound, wherein the Co salt, the Mn salt, the lanthanide salt and the Br are 500 (200-300) (20-110) (1000-2000).
In the above technical solution, the bromine-containing compound is preferably at least one selected from inorganic bromides and brominated hydrocarbons.
In the above technical solution, the Co salt is preferably cobalt acetate.
In the above technical solution, the Mn salt is preferably manganese acetate.
In the above technical solution, the lanthanide salt is at least one of a cerium salt and a lanthanum salt.
In the above technical solution, the lanthanide salt further preferably includes both a cerium salt and a lanthanum salt, and the two salts have a synergistic effect in reducing the contents of by-products HMBA, 4-CBA and p-TA.
In the above technical solution, the inorganic bromide is preferably selected from hydrogen bromide or an alkali metal bromide.
In the above technical solution, the brominated hydrocarbon is preferably at least one selected from tetrabromoethane, tetrabromopropane and tetrabromobutane. Wherein the specific substitution position of the bromine in the brominated hydrocarbon is not particularly limited. The brominated hydrocarbon is, for example, but not limited to, at least one selected from the group consisting of 1,1,2, 2-tetrabromoethane, 1,1,1, 2-tetrabromoethane, 1,1,2, 2-tetrabromopropane and 2,2,3, 3-tetrabromobutane.
In the above technical scheme, the material may further comprise anthraquinone disulfonic acid, wherein the total weight of the Co salt, Mn salt, lanthanide salt, Br and anthraquinone disulfonic acid is 500 (200-300), 20-110, 1000-2000 and 5-20.
In the above technical scheme, the anthraquinone disulfonic acid is preferably at least one selected from anthraquinone-1, 5-disulfonic acid and anthraquinone-2, 7-disulfonic acid.
In the technical scheme, the anthraquinone disulfonic acid further preferably simultaneously comprises anthraquinone-1, 5-disulfonic acid and anthraquinone-2, 7-disulfonic acid, and the two have synergistic effect on the aspect of reducing the contents of by-products HMBA, 4-CBA and p-TA.
To solve the second technical problem, the technical solution of the present invention is as follows: a process for producing an aromatic polycarboxylic acid by liquid-phase oxidation, said process comprising reacting a polyalkyl-substituted aromatic hydrocarbon with an oxidizing agent in the presence of a catalyst as described in any one of the preceding technical problems, using acetic acid as a solvent, to obtain the aromatic polycarboxylic acid.
In the above technical solution, the oxidizing agent is preferably a gas containing elemental oxygen. Such as, but not limited to, oxygen, air, oxygen nitrogen mixtures, oxygen air mixtures, oxygen nitrogen mixtures, and the like.
In the technical scheme, the aromatic hydrocarbon in the polyalkyl-substituted aromatic hydrocarbon is preferably benzene or naphthalene.
In the technical scheme, the polyalkyl substituted arene is preferably dialkyl substituted arene.
In the above technical scheme, the alkyl group in the polyalkyl-substituted aromatic hydrocarbon is preferably C1～C4Such as, but not limited to, methyl, ethyl, or propyl.
In the above technical schemes, the polyalkyl aromatic hydrocarbon is, by way of example and not limitation, p-xylene and m-xylene.
In the technical scheme, the reaction temperature is preferably 160-250 ℃.
In the technical scheme, the reaction pressure is preferably 0.8-2.0 MPa.
In the technical scheme, the reaction time is preferably 1-5 h.
In the above technical scheme, the oxidant for the reaction is preferably air, and the space velocity (the ratio of the gas volume flow rate to the volume of the reactant) is 2-5 h-1。
It will be readily understood by those skilled in the art that the number of aromatic polycarboxylic acids obtained by the above method is the same as the number of alkyl groups in the polyalkyl-substituted aromatic hydrocarbon molecule employed.
In the products of the examples and comparative examples of the present invention, the sample to be analyzed was first completely dissolved in dimethyl sulfoxide, PX was analyzed by gas chromatography, and other substances were analyzed by High Performance Liquid Chromatography (HPLC).
Compared with the traditional catalyst, the method for preparing the terephthalic acid by oxidizing the p-xylene reduces the bromine consumption by more than 30 percent (the bromine content of the BP-Mitsui process is 1500ppmw), the yield of the terephthalic acid reaches more than 96 percent, and a better effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ with air airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 2 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw La2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ with air airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 3 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、15ppmw Ce4+、15ppmw La2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ with air airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is analyzed on line by infrared rayOxygen content is controlled to be 3-6 wt%, and CO2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 4 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-1, 5-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 5 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-2, 7-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 6 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-1, 5-disulfonic acid, 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-2, 7-disulfonic acid, uniformly mixing, and adding into an autoclaveAnd sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 7 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-1, 5-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃Air space velocity of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 8 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-2, 7-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 9 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw La2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-1, 5-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 10 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw La2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-2, 7-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 11 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrakisBromoethane (bromine is 1000ppmw based on the whole solution), anthraquinone-1, 5-disulfonic acid (2.5 ppmw based on the whole solution) and anthraquinone-2, 7-disulfonic acid (2.5 ppmw based on the whole solution) are uniformly mixed, added into an autoclave and sealed.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 12 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、30ppmw La2+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-2, 7-disulfonic acid and 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-1, 5-disulfonic acid, uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 13 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、15ppmw La2+、15ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-1, 5-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 14 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、15ppmw La2+、15ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution) and 5ppmw of anthraquinone-2, 7-disulfonic acid (based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is analyzed on line by infrared ray,the tail oxygen content is controlled to be 3-6 wt%, and CO2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
[ example 15 ]
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+、15ppmw La2+、15ppmw Ce4+) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-2, 7-disulfonic acid and 2.5ppmw (bromine is 1000ppmw based on the whole solution) of anthraquinone-1, 5-disulfonic acid, uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
Comparative example 1
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+. ) And 0.55g of 1,1,2, 2-tetrabromoethane (bromine is 1000ppmw based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
Comparative example 2
The reaction was carried out in a 1000ml autoclave made of titanium material with a magnetic stirrer, gas feed line, reflux condenser, thermocouple, rupture disk, with a stirring speed of 400rpm, heated by circulating hot oil. The reaction steps are as follows:
1) 80g of p-xylene, 400g of acetic acid and 20g of metal acetate (500 ppmw Co based on the total solution) were weighed out2+、250ppmw Mn2+. ) And 0.83g of 1,1,2, 2-tetrabromoethane (the bromine content is 1500ppmw based on the whole solution), uniformly mixing, adding into an autoclave, and sealing.
2) Adding 2.0MPa nitrogen gas to carry out airtight test for 30min, and determining that the pressure drop is not more than 0.1MPa within 30 min.
3) Adding nitrogen at a space velocity of 4h-1And the stirrer was started at a stirring speed of 400rpm and the temperature was raised to 186 ℃ while maintaining the pressure at 1.0 MPa.
4) Switching with air at 186 ℃ and airspeed of 4h-1The reaction was carried out for 120min while maintaining the temperature.
5) And after the reaction, switching to nitrogen again, cooling to room temperature, relieving the pressure of the reaction kettle to normal pressure, adding dimethyl sulfoxide to completely dissolve the solid, taking out the solid, analyzing unreacted p-xylene by using gas chromatography, and analyzing Terephthalic Acid (TA), p-toluic acid (p-TA), p-methylhydroxybenzoic acid (HMBA) and p-aldehyde benzoic acid (4-CBA) by using high performance liquid chromatography.
The tail gas is subjected to infrared online analysis, the tail oxygen content is controlled to be 3-6 wt%, and CO is2The content is controlled to be 1.0-1.5 wt%, the formula of the catalyst is shown in table 1, and the analysis result of main impurities in the product is shown in table 2.
TABLE 1
TABLE 2
| PX(wt％) | HMBA(wt％) | 4-CBA(wt％) | p-TA(wt％) | |
| Example 1 | 0 | 0.20 | 3.0 | 1.85 |
| Example 2 | 0 | 0.21 | 3.1 | 1.83 |
| Example 3 | 0 | 0.16 | 1.8 | 1.30 |
| Example 4 | 0 | 0.20 | 2.8 | 1.50 |
| Example 5 | 0 | 0.21 | 2.9 | 1.51 |
| Example 6 | 0 | 0.15 | 1.7 | 1.00 |
| Example 7 | 0 | 0.11 | 1.3 | 0.85 |
| Example 8 | 0 | 0.12 | 1.3 | 0.79 |
| Example 9 | 0 | 0.12 | 1.2 | 0.78 |
| Example 10 | 0 | 0.11 | 1.1 | 0.70 |
| Example 11 | 0 | 0.06 | 0.72 | 0.45 |
| Example 12 | 0 | 0.05 | 0.73 | 0.44 |
| Example 13 | 0 | 0.04 | 0.52 | 0.40 |
| Example 14 | 0 | 0.05 | 0.50 | 0.38 |
| Example 15 | 0 | 0 | 0.36 | 0.24 |
| Comparative example 1 | 0.10 | 0.30 | 4.4 | 2.0 |
| Comparative example 2 | 0 | 0.15 | 1.6 | 1.8 |
Claims (10)
1. The catalyst for preparing the aromatic polycarboxylic acid by liquid-phase oxidation comprises Co salt, Mn salt, lanthanide salt, anthraquinone disulfonic acid and a bromine-containing compound, wherein the weight percentages of Co, Mn, lanthanide element, Br, anthraquinone disulfonic acid are 500 (200-300) (20-110) (1000-2000) (5-20).
2. The catalyst according to claim 1, wherein the bromine-containing compound is at least one selected from the group consisting of inorganic bromides and brominated hydrocarbons.
3. The catalyst of claim 1 wherein said Co salt is cobalt acetate.
4. The catalyst of claim 1, wherein the Mn salt is manganese acetate.
5. The catalyst of claim 1, characterized in that the lanthanide salt is at least one of a cerium salt and a lanthanum salt.
6. The catalyst of claim 2, characterized in that the inorganic bromide is selected from hydrogen bromide or an alkali metal bromide.
7. The catalyst of claim 2, wherein the brominated hydrocarbon is at least one member selected from the group consisting of tetrabromoethane, tetrabromopropane, and tetrabromobutane.
8. The catalyst according to claim 1, wherein the anthraquinone disulfonic acid is at least one member selected from the group consisting of anthraquinone-1, 5-disulfonic acid and anthraquinone-2, 7-disulfonic acid.
9. A method for producing aromatic polycarboxylic acid by liquid phase oxidation, which comprises the step of reacting polyalkyl-substituted aromatic hydrocarbon with an oxidant in the presence of a catalyst according to any one of claims 1 to 8 by using acetic acid as a solvent to obtain the aromatic polycarboxylic acid.
10. The method of claim 9, wherein the oxidizing agent is an elemental oxygen-containing gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610750944.XA CN107774315B (en) | 2016-08-29 | 2016-08-29 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610750944.XA CN107774315B (en) | 2016-08-29 | 2016-08-29 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107774315A CN107774315A (en) | 2018-03-09 |
| CN107774315B true CN107774315B (en) | 2020-09-04 |
Family
ID=61441358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610750944.XA Active CN107774315B (en) | 2016-08-29 | 2016-08-29 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107774315B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645812A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Start-up method for preparing terephthalic acid by liquid-phase oxidation of paraxylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453538A (en) * | 1994-02-14 | 1995-09-26 | Amoco Corporation | Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio |
| CN1802210A (en) * | 2003-06-06 | 2006-07-12 | Bp北美公司 | Oxidation of aromatic hydrocarbons using brominated anthracene promoters |
| CN102909079A (en) * | 2012-05-31 | 2013-02-06 | 中国石油化工股份有限公司 | Methyl aromatics oxidation catalyst system |
-
2016
- 2016-08-29 CN CN201610750944.XA patent/CN107774315B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5453538A (en) * | 1994-02-14 | 1995-09-26 | Amoco Corporation | Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio |
| CN1802210A (en) * | 2003-06-06 | 2006-07-12 | Bp北美公司 | Oxidation of aromatic hydrocarbons using brominated anthracene promoters |
| CN102909079A (en) * | 2012-05-31 | 2013-02-06 | 中国石油化工股份有限公司 | Methyl aromatics oxidation catalyst system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107774315A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8884054B2 (en) | Process for oxidizing alkyl aromatic compounds | |
| US9266809B2 (en) | Process for producing terephthalic acid | |
| US9045407B2 (en) | Mixtures used in oxidizing alkyl aromatic compounds | |
| TWI723950B (en) | Pressurized crude aromatic carboxylic acid feed mixes | |
| US8835678B2 (en) | Solid terephthalic acid composition | |
| CN107774316B (en) | Liquid phase oxidation synthesis aromatic polycarboxylic acid catalyst | |
| CN107282103B (en) | Catalyst for producing aromatic polycarboxylic acids | |
| CN107175128B (en) | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation | |
| CN107774315B (en) | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation | |
| CN112645812A (en) | Start-up method for preparing terephthalic acid by liquid-phase oxidation of paraxylene | |
| CN111068782B (en) | Catalyst for producing aromatic polycarboxylic acid by liquid phase oxidation and application thereof | |
| CN107790179B (en) | Catalyst for producing aromatic polycarboxylic acid by liquid phase oxidation | |
| CN107442167B (en) | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation | |
| CN106423294B (en) | Liquid phase oxidation prepares catalyst used in polycarboxylic aromatic acids | |
| CN112441908B (en) | Method for synthesizing 2,6-naphthalene dicarboxylic acid | |
| CN112441910A (en) | Method for synthesizing aromatic polycarboxylic acid by liquid-phase oxidation | |
| CN114054085B (en) | Catalyst composition and method for synthesizing isophthalic acid by oxidizing metaxylene | |
| CN112645811A (en) | Method for preparing 2,6-naphthalene dicarboxylic acid by oxidizing 2, 6-diisopropyl naphthalene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |